EP2278033B1 - Alliage de cuivre blanc-argent et son procédé de fabrication - Google Patents

Alliage de cuivre blanc-argent et son procédé de fabrication Download PDF

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EP2278033B1
EP2278033B1 EP09720811.0A EP09720811A EP2278033B1 EP 2278033 B1 EP2278033 B1 EP 2278033B1 EP 09720811 A EP09720811 A EP 09720811A EP 2278033 B1 EP2278033 B1 EP 2278033B1
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phases
mass
heat treatment
cold
subjected
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EP2278033A1 (fr
EP2278033A4 (fr
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Keiichiro Oishi
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Mitsubishi Shindoh Co Ltd
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Mitsubishi Shindoh Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • the present invention relates to a copper alloy having a silver-white color equivalent to that of nickel silver and a method of producing the same.
  • Copper alloys such as brass are variously used for piping materials, building materials, electric and electronic devices, machine parts, and the like.
  • a white (silver-white) color tone may be required.
  • copper alloy products are subjected to a plating process such as nickel-chrome plating.
  • the plated products have the problem that the plating layer of the surface is peeled off with extended use, and there is a problem in the case of reuse, since when the plated products are re-melted the plating material mixes with the copper alloy and decreases quality.
  • a Cu-Ni-Zn alloy representing a lustrous white color on its own has been proposed.
  • Non-Patent Citation 1 free-cutting nickel silver containing Cu (60.0 to 64.0 mass%), Ni (16.5 to 19.5 mass%), Pb (0.8 to 1.8 mass%), Zn (remainder), and the like is prescribed.
  • Patent Citation 1 a white-based copper alloy containing Cu (41.0 to 44.0 mass%), Ni (10.1 to 14.0 mass%), Pb (0.5 to 3.0 mass%), and Zn (remainder) is disclosed.
  • JP H01-177327 discloses a silver-white copper-based alloy containing Ni (6-15 mass%), Mn (3-8 mass%), Pb (0.1-2.5 mass%) and Zn (31-47 mass%) and the balance consisting of Cu with inevitable impurities.
  • the copper alloy contains a large amount of Ni and Pb causing health and sanitation problems, and the use thereof is restricted. That is, among metal allergies Ni is the cause of a particularly fierce Ni allergy, and Pb is a known hazardous substance. Accordingly, there is a problem with use in direct contact with the skin of a human body as a key or a similar object.
  • the copper alloy contains a large amount of Ni. Accordingly, workability such as its hot rolling properties, machinability, and pressing properties deteriorates; Ni is expensive, raising production costs, and thus its use is restricted from these viewpoints.
  • An object of the invention is to provide a silver-white copper alloy which represents a silver-white color equivalent to that of nickel silver and has excellent hot processing properties and the like, and to provide a method of producing a silver-white copper alloy capable of appropriately producing the silver-white copper alloy.
  • the invention proposes the following silver-white cooper alloy and a method of producing the same.
  • the invention provides a silver-white copper alloy as defined in claim 1.
  • [a] denotes a dimensionless value of a content of an element a
  • the content of the element a is represented by [a] mass%.
  • a content of Cu is [Cu] mass%.
  • the content of ⁇ phases depends on an area ratio, and a dimensionless value of the content is represented by [ ⁇ ]. That is, the content (area ratio or area containing ratio) of the ⁇ phases is represented by [ ⁇ ]%.
  • the area ratio that is the content of the ⁇ phases is measured by image analysis.
  • the area ratio is obtained by binarizing a 100-fold magnification optical microscope photography as for a hot processed material and a cast material, and binarizing a 200-fold or 500-fold magnification optical microscope structure, mainly, a metal structure analyzed by FE-SEM-EBSP for a final product (hot processed material, continuously cast material), using the image processing software "WinROOF" (Tech-Jam Co. Ltd).
  • the area ratio is an average value of an area ratio measured at two predetermined positions and three fields of view.
  • the copper alloy is provided as a hot processed material formed by performing one or more heat treatments and cold processes (rolling process) on a hot processed raw material subjected to a hot process (rolling process, extruding process), or as a continuously cast material formed by performing one or more heat treatments and cold processes on a cast raw material (continuously cast raw material) obtained by continuous casting.
  • the copper alloy is appropriately used as a constituent material of a key, a key blank, or a press product.
  • an average grain size of ⁇ phases is 0.003 to 0.018 mm
  • an average area (hereinafter, referred to as " ⁇ phase area”) of ⁇ phases is 4 ⁇ 10 -6 to 80 ⁇ 10 -6 mm 2
  • an average value (hereinafter, referred to as "long side/short side ratio") of long side/short side of ⁇ phases is 2 to 7.
  • the average area ( ⁇ phase area) of ⁇ phases is a value obtained by dividing the total area of ⁇ phases by the number of ⁇ phases in a specific cross section of the copper alloy.
  • the specific cross section is a cross section parallel in a lengthwise direction (rolling direction) of the plate-shaped material and perpendicular to a surface (or back surface) of the plate-shaped material.
  • two specific cross sections are cross sections at positions of t/3 and t/6 (t is a plate thickness) from the surface of the plate-shaped material.
  • a cross section (cross section parallel in an extruding direction and a drawing direction) parallel to an axial line of the cylindrical material is set as the specific cross section.
  • two specific cross sections are parallel cross sections at positions d/3 and d/6 (d is a diameter of a circular cross section perpendicular to the axial line of the cylindrical material).
  • the long side of ⁇ phases is a length of a longitudinal direction (direction parallel to the longitudinal direction (rolling direction) in plate-shaped material, and direction parallel to the axial direction (extruding direction, drawing direction) in the cylindrical material) of the specific cross section
  • the short side of ⁇ phases is a length of a direction perpendicular to the long side in the specific cross section.
  • the average value of long side/short side of ⁇ phases is an average value of long side/short side of ⁇ phases obtained in each specific cross section.
  • a ratio (hereinafter, referred to as a 12 or less ⁇ phase ratio) of ⁇ phases in which the value of long side/short side is 12 or less to the whole ⁇ phases is 95% or more, or the number of ⁇ phases having the long side of 0.06 mm or more is not more than 10 per 0.1 mm 2 .
  • the length (long side, short side) of ⁇ phases is observed and measured with a 200-fold or 500-fold magnification optical microscope structure, mainly, a metal structure analyzed by FE-SEM-EBSP with respect to the final product (hot processed material, continuously cast material), when the specific cross section is observed (field of view of 50x100 mm) with a metal structure measured by a 100-fold magnification optical microscope with respect to a hot processed material and a cast material.
  • a 200-fold or 500-fold magnification optical microscope structure mainly, a metal structure analyzed by FE-SEM-EBSP with respect to the final product (hot processed material, continuously cast material), when the specific cross section is observed (field of view of 50x100 mm) with a metal structure measured by a 100-fold magnification optical microscope with respect to a hot processed material and a cast material.
  • Fe and/or Si are contained as inevitable impurities.
  • the content of Fe is 0.3 mass% or less and the content of Si is 0.1 mass% or less.
  • a small amount of Co is considered as being encompassed in Ni according to JIS or the like. Accordingly, for example, when the content of Co is about 0.1%, Co is considered as inevitable impurities.
  • the present invention further provides a method of producing the copper alloy of claim 1. That is, the invention provides a method of producing a silver-white copper alloy (hereinafter, referred to as "rolling production method"), by which a hot processed material that is the copper alloy is obtained by performing one or more heat treatments (heating temperature: 600 to 760°C, heating time: 2 to 36 hours, average cooling rate down to 500°C: 1°C/minute or less) and cold processes on a hot processed raw material formed by performing a hot process (hot rolling, hot extruding, etc.) on an ingot, and provides a method of a silver-white copper alloy (hereinafter, “casting production method”), by which a continuously cast material that is the copper alloy is obtained by performing one or more heat treatments (heating temperature: 600 to 760°C, heating time: 2 to 36 hours, average cooling rate down to 500°C: 1°C/minute or less) and a cold process on a cast raw material obtained by continuous casting.
  • rolling production method a method of producing a
  • a processing rate in the first cold process performed on the first heat treated material subjected to the heat treatment is 25% or more.
  • the material is made into a predetermined size and shape by the first heat treatment while reducing ⁇ phases generated in the producing step (step of hot rolling or casting) of the raw material.
  • a slight cold process in which a processing rate does not reach 25% may be performed on the raw material (hot processed raw material, cast raw material) before performing the first heat treatment.
  • a cold process is not a first cold process in the rolling production method or casting production method.
  • a hot process may be performed on the raw material after performing the slight cold process in which the processing rate does not reach 25%.
  • this heat treatment is considered as the first heat treatment.
  • the heating process in the second heat treatment or the later heat treatment heat treatment performed after the first cold process
  • the processing rate of the cold process performed after the last heat treatment is 50% or less.
  • Cu is a primary element that is the basis of determining all characteristics in the copper alloy, and is balanced with the other contained elements Zn, Ni, and Mn.
  • ⁇ phases are excessively increased and thus ductility or cold processing property (cold rolling property) deteriorates.
  • ductility or cold processing property cold rolling property
  • tarnish resistance and stress corrosion cracking resistance are decreased, and also press formability is decreased.
  • the content of Cu exceeds 50.5 mass%, the amount of ⁇ phases is reduced, strength is decreased, torsion strength, wear resistance, press formability, and machinability are decreased, and hot ductility or hot casting property is decreased.
  • the content of Cu is necessarily 47.5 to 50.5 mass%, and preferably 47.9 to 49.9 mass%.
  • the content of Cu is most preferably 48.0 to 49.6 mass%
  • the content of Cu is most preferably 48.2 to 49.8 mass%.
  • Zn is a primary element equivalent to Cu and is an important element to secure characteristics of the copper alloy. For example, Zn improves mechanical strength such as tensile strength and proof strength, and Zn is the remainder remaining by subtracting the content of the other contained elements from the whole content, considering the relationship with the other contained elements. The remainder does not include inevitable impurities.
  • Ni is an important element to secure the white color (silver-white color) of the copper alloy.
  • Ni is contained exceeding a predetermined amount, yield (surface crack, edge crack) of hot rolling deteriorates even when there are a great number of ⁇ phases. Accordingly, flowability/ castability at the time of casting deteriorates, and press formability and machinability are decreased.
  • the content of Ni is excessive, soft yellow tone of the copper alloy is damaged by getting whiter, even though it depends also on a composition amount of Mn.
  • Ni is an expensive element, and an allergen (Ni allergy). Accordingly, it is preferable to reduce the content of Ni.
  • Ni there is a limit in reducing the content of Ni to secure color tone, tarnish resistance, and stress corrosion cracking resistance of the copper alloy. From this viewpoint, the content of Ni is necessarily 7.8 to 9.8 mass%, preferably 8.2 to 9.6 mass%, and most preferably 8.4 to 9.5 mass%.
  • color tone of the copper alloy depends on a composition ratio of Mn with Ni, but Mn serves as a Ni substituting element to obtain white color property while a slight yellow tone remains.
  • Mn improves torsion strength and wear resistance, and improves press property and machinability though depending on the relation with ⁇ phases. Independent Mn hardly contributes to tarnish resistance or stress corrosion cracking resistance, and has a large negative effect. Accordingly, a combination with Ni is important.
  • the content of Mn is necessarily 4.7 to 6.3 mass%, preferably 5.0 to 6.2 mass%, and most preferably 5.2 to 6.2 mass%.
  • the relationship of f1 is important for securing hot processing property (hot rolling, hot extruding) and cold processing property (cold rolling), while improving press formability, machinability, torsion strength, bending processing property, tarnish resistance, and stress corrosion cracking resistance.
  • the copper alloys are produced by a casting production method
  • a ratio occupied by ⁇ phases in a high temperature structure in an optimal composition is about 70% (55 to 85%) at 800°C corresponding to the initial temperature of a hot rolling process.
  • the ratio is about 40% (25 to 60%) at 700°C corresponding to the middle period of the hot rolling process, and is about 20% (3 to 40%) at 600°C corresponding to the final rolling temperature.
  • the hot process of Cu-Zn alloy including Ni is easily performed (improves the hot processing property) and characteristics of the final products are improved.
  • f2 is less than 0.49
  • the ⁇ phases are not greatly changed as described above. That is, there is a little change of ⁇ phases with respect to the change in temperature.
  • the ratio occupied by ⁇ phases is 45% at 800°C, 35% at 700°C, and 25% at 600°C.
  • the value of f4 is less than the lower limit of the range, the yellow tone is too strong, it is difficult to obtain a proper silver-white color, and there are problems in tarnish resistance and stress corrosion cracking resistance.
  • a zinc concentration of ⁇ phases of Cu-Zn alloy is higher than that of ⁇ phases by 6%, and a crystal structure thereof is different from that of ⁇ phases. For this reason, hardness of ⁇ phases is high (several ten points in Vickers hardness), but ⁇ phases are softer than ⁇ phases (elongation value of ⁇ phases is 1/10 of ⁇ phases).
  • Such property of ⁇ phases is changed by an additional element of several % or more according to the added element. As described above, when a large amount of Ni and/or Mn is added at 10% or more in total, the property of ⁇ phases is inevitably changed.
  • ⁇ phases In the metal structure, there is naturally a problem in distribution of ⁇ phases. A predetermined regular size and the uniform distribution thereof are important (in machinability, press formability, strength, torsion strength, wear resistance, ductility, and the like). ⁇ phases are subjected more to corrosion than ⁇ phases, so the continuous presence of ⁇ phases causes corrosion or tarnish. A ratio occupied by ⁇ phases has an influence on all characteristics such as press formability and machinability. It is insufficient to determine only the ratio occupied by ⁇ phases, and thus formation and distribution of ⁇ phases are important. When the ratio of ⁇ phases is less than 2%, press formability and machinability are insufficient.
  • ⁇ phases The shape of ⁇ phases is one of the most important factors. Press formability and machinability are not significantly improved but for the reason of only the large amount of ⁇ phases. Rather, when there is too large an amount of hard ⁇ phases, durability and the like of a cutting tool are decreased, and further naturally, bending property, strength against impact, and cold processing property are decreased. Immediately after a hot process, ⁇ phases represent a network-shaped metal structure continuously in a rolling direction or extruding direction, and the amount thereof is large. The same holds true for a cast material.
  • the stress concentration source with regard to machinability is hard ⁇ phases at the time of cutting, and thus dividing or shearing deformation of chips caused by ⁇ phases is made easy.
  • a ratio (hereinafter, referred to as " ⁇ phase ratio”) occupied by ⁇ phases in the whole phase structure of the copper alloy is necessarily 2 to 17%, preferably 3 to 15%, and most preferably 4 to 12%.
  • an average area of ⁇ phases is preferably 4 ⁇ 10 -6 to 80 ⁇ 10 -6 mm 2 , more preferably 6 ⁇ 10 -6 to 40 ⁇ 10 -6 mm 2 , and most preferably 8 ⁇ 10 -6 to 32 ⁇ 10 -6 mm 2 .
  • a ratio of long side/short side is preferably 2 to 7, more preferably 2.3 to 5, and most preferably 2.5 to 4.
  • the ⁇ phase ratio equal to or less than 12 is preferably 95% or more, and more preferably 97% or more.
  • the number of ⁇ phases having a long side of 0.06 mm or more per 0.1 mm 2 in the specific cross section is not more than 10 (preferably below 5).
  • ⁇ phase size an average grain size of ⁇ phases (hereinafter, referred to as " ⁇ phase size” is 0.003 to 0.018 mm, preferably 0.004 to 0.015 mm, and more preferably 0.005 to 0.012 mm.
  • a metal structure (metal structure of hot processed raw material or continuously cast raw material) after the hot rolling, hot extruding, and continuous casting is a net-like shape (network shape) in which ⁇ phases are connected. ⁇ phases are excessively present (remained) to obtain satisfactory hot processing property.
  • it is difficult to obtain satisfactory press formability, machinability, torsion strength, and wear resistance as well as impact resistance, corrosion resistance, and tarnish resistance.
  • a cold process (rolling) at a large processing rate is performed, cracks easily occur.
  • the net-like P phases are finely dispersed at the final step of the process of the rolling production method or casting production method, and thus excellent press formability or the like is obtained.
  • the raw material hot processed raw material, continuously cast raw material
  • the cold processed material is subjected to a heat treatment at 550 to 745 °C for 2 to 36 hours and is then slowly cooled at an average cooling rate of 1°C/minute or less down to 500°C.
  • the temperature of the heat treatment is higher than an annealing temperature of general copper alloys, because the net-shaped metal structure is not easily dissolved once it is no longer at a high temperature.
  • the second heat treatment or the later heat treatment performed after a cold process also serves as recrystallization annealing of the cold processed material.
  • the copper alloy has a metal structure including ⁇ phases. Since the ⁇ phase area is expanded on the high temperature side due to the addition of Mn, coarsening of ⁇ phase does not occur. In a case of a plate-shaped material having a plate thickness of about 2 to 3.5 mm, it is preferable to perform this heat treatment more than twice including the first heat treatment.
  • the first heat treatment that is, a heat treatment of a hot processed raw material or continuously cast raw material.
  • the advantage is that only one more process of heat treatment is required in a case of hot rolling or horizontal continuous casting where, as the next process, there is a milling process (sculpting) to mechanically cut away oxidized coating and in a case of hot extrusion, a process to clean it away.
  • the first heat treatment is performed on a raw material having almost no distortion, resulting in a low diffusion rate and a low rate of change in structure.
  • the heat treatment is performed at 550 to 745°C as described above, but it is performed preferably at 610 to 730°C, and more preferably the material should be kept at 630 to 690°C for 4 to 24 hours, and then be slowly cooled down to 500°C at a cooling rate of 1°C/minute or less (preferably 0.5°C/minute or less). In addition, it is also preferable that the material is slowly cooled down to 500 to 550°C and then is kept at the temperature (500 to 550°C) for 1 to 2 hours.
  • the net-shaped ⁇ phases are divided by the precipitation of ⁇ phases, the area ratio occupied by the ⁇ phases is decreased, and the grain size of the ⁇ phase becomes about 0.015 to 0.050 mm.
  • the aforesaid ratio occupied by the ⁇ phases should be 3 to 24% (preferably 4 to 19%, more preferably 5 to 15%) since after the net-shaped structure of ⁇ phases is broken by the precipitation of ⁇ phases.
  • the net-shaped structure should be broken, an average value of long side/short side of the ⁇ phases be 2 to 18 (preferably 2.5 to 15), and the area ratio of ⁇ phases having the value of long side/short side more than 20 be 30% or less (preferably 20% or less).
  • the number of ⁇ phases per 1 mm 2 having a length of 0.5 mm or more should be within less than 10 (preferably within less than 5).
  • a diffusion rate is lower, and thus it is preferable to perform a heat treatment at 620 to 760°C for 4 to 24 hours. More preferably, the heat treatment is performed at 630 to 750°C, and then the material is slowly cooled down to at least 500°C at an average cooling rate of 1°C/minute or less (preferably 0.5°C/minute or less). After the slow cooling down to 500 to 550°C, it is effective to keep the material at that temperature for 1 to 2 hours.
  • a thickness of a hot rolling plate and continuously cast material is generally about 10 to 15 mm or about 20 mm, the thickness is reduced by cold rolling to be thinner and another heat treatment is performed.
  • the temperature at that time is preferably 550 to 625°C for 2 to 16 hours, and more preferably 555 to 610°C.
  • the divided ⁇ phases are elongated again in the rolling direction by cold rolling, and the ⁇ phases are uniformly divided again by this heat treatment while reducing the ⁇ phase amount by the precipitation of ⁇ phases.
  • the growth of grains is suppressed by the addition of Ni and/or Mn in a predetermined condition and the proper amount of ⁇ phases.
  • the average grain sizes of ⁇ phases is controlled to be 0.003 to 0.018 mm (preferably 0.004 to 0.015 mm, and more preferably 0.005 to 0.012 mm).
  • the average grain size of ⁇ phases is necessarily 0.018 mm or less, and preferably 0.015 mm or less in consideration of press formability (particularly shear droop, surface roughness), machinability, ductility, and the other properties.
  • press formability particularly shear droop, surface roughness
  • machinability machinability
  • ductility ductility
  • ⁇ phases which are longitudinally elongated by a previously performed cold process, are not divided sufficiently.
  • the ⁇ phases are in a non-recrystallization state at a temperature at 540°C or lower (particularly 500°C or lower).
  • ⁇ phases precipitates around grain boundaries.
  • the precipitated ⁇ phases are not so much effective in press property and machinability, and rather deteriorate bendability and impact properties. Over 625°C, ⁇ phases become too large and ⁇ phases are further divided.
  • the ⁇ phases become excessively refined (long side/short side ratio (average value of long side/short side) becomes too small), and particularly have a negative influence on press formability and machinability. Accordingly, it is necessary to perform the heat treatment under the above-described conditions, the material should be kept at 550 to 625°C for 2 to 16 hours, preferably at 555 to 610°C for 2 to 16 hours, then be cooled down to 500°C at a cooling rate of 1°C/minute or less and, most preferably, be kept at 560 to 600°C for 2 to 16 hours, then slowly cooled down to 500°C preferably at a cooling rate of 0.5°C/minute or less.
  • Pb, Bi, C, and S contained in the copper alloy have a function of effectively improving press formability and machinability at a lower concentration by the heat treatment.
  • Pb, Bi, C, and S are hardly solid-solution into Cu-Zn-Ni alloy.
  • a very small amount could be solid-solution.
  • these elements exist in the phase boundaries of ⁇ and ⁇ or mostly in ⁇ phases in a solid solution state.
  • ⁇ phases and ⁇ phases Mainly in phase boundaries of ⁇ phases and ⁇ phases, some or most of these elements are subjected to solid solution and/or uneven distribution in an over-saturated state, for a hot rolling material, hot extruding material, and a cast material having the claimed composition, particularly, close to the lower limit.
  • ⁇ phases are reorganized by the precipitation of ⁇ phases.
  • the unevenly distributed elements in solid solution such as Pb are precipitated as particles of Pb, Bi, and C, and as compounds of Mn and S in case of S.
  • the heat treatment it is understood that it is preferable to perform the heat treatment at about 670°C (620 to 710°C).
  • the second heat treatment because the amount of ⁇ phases is decreased as compared with the first heat treatment, the ⁇ phases are divided and a plasticity process is added, the precipitation of Pb, Bi, C, and the like from ⁇ phases is further promoted by performing the heat treatment at a lower temperature (about 580°C), and minute grains are formed.
  • Pb, Bi, C, and S have a function of further improving machinability, press formability, and wear resistance with a small amount.
  • these elements are minutely precipitated or crystallized as Pb particles, Bi particles, and C particles, and as MnS compounds by coupling with mainly Mn with respect to S.
  • these particles Pb particles, Bi particles, C particles, and MnS compounds
  • Pb particles, Bi particles, C particles, and MnS compounds are increased too much, there is a negative influence on impact property, torsion strength, ductility, and hot/cold processing property.
  • problems occur to human bodies of, for example, key users.
  • the contents are equal to or less than the predetermined value, the improving effect in press formability, machinability, and the like are not exhibited but there is no negative influence on properties such as strength and ductility.
  • Pb, Bi, C, and S are contained within predetermined content ranges. That is, the content of Pb is 0.001 to 0.08 mass%, preferably 0.0015 to 0.03 mass%, and more preferably 0.002 to 0.014 mass%.
  • the content of Bi is 0.001 to 0.08 mass%, preferably 0.0015 to 0.03 mass%, and more preferably 0.002 to 0.014 mass%.
  • the content of C is 0.0001 to 0.009 mass%, preferably 0.0002 to 0.006 mass%, and more preferably 0.0005 to 0.003 mass%.
  • the content of S is 0.0001 to 0.007 mass%, preferably 0.0002 to 0.003 mass%, and more preferably 0.0004 to 0.002 mass%.
  • a numerical value "0.001" of a minus value for example, a value of "-0.001” substantially corresponds to a solid solution amount (0.001 mass%) in industrial production of Pb, Bi, C, S, and the like through the heat treatment processes of the invention, that is, in practical use of the invention, and a plus square root over the solid solution amount contributes to properties.
  • the value is less than the lower limit, press formability or machinability is not industrially satisfied even when the influence element such as Pb is added.
  • the value is more than the upper limit, impact property or bending property deteriorates and thus it is not suitable for a key or the like.
  • Al, P, Zr, and Mg contained in the third and fourth copper alloys have a function of improving properties in the step of casting materials, for example, improving fluidity of melt flow, as well as improving strength and tarnish resistance, improving a refinement of metal structure, and uniformly distributing phases.
  • the content of P is 0.001 to 0.09 mass%, and preferably 0.003 to 0.08 mass%
  • the content of Zr is 0.005 to 0.035 mass%, and preferably 0.007 to 0.029 mass%
  • the content of Al is 0.01 to 0.5 mass%, and preferably 0.02 to 0.3 mass%.
  • the functions of improving fluidity of melt flow, tarnish resistance and strength are saturated.
  • ductility or torsion strength deteriorates, and thus cracks easily occur in a cold process.
  • Zr and P among these elements are added together, a macrostructure becomes refined particularly in the step of a cast material and ⁇ phases becomes uniformly distributed.
  • P is contained preferably by 0.03 to 0.09 mass%
  • Zr is contained preferably by 0.007 to 0.035 mass%
  • a value of [P]/[Zr] is 1.4 to 7, and preferably 1.7 to 5.1.
  • a size or shape of ⁇ phases of a final product is in a more preferable state.
  • a continuously cast raw material is not subjected to a hot process, and thus coarsened net-shaped ⁇ phases are easily formed. Accordingly, it is effective to add P and Zr together.
  • Si and Fe may be inevitably mixed as impurities.
  • Fe when Fe is precipitated in a content of more than 0.3 mass%, Fe has a negative influence on press formability, machinability, and the other properties.
  • the precipitation of Fe when the precipitation of Fe is equal to or less than 0.2 mass%, there is no influence on the properties.
  • Si when the content of Si is equal to or more than 0.1 mass%, Si is coupled with Ni or Mn to form a silicon compound, thereby having a negative influence on press formability, machinability, and the other properties.
  • the content of Si is equal to or less than 0.05 mass%, there is no influence on the properties.
  • the copper alloy as a silver-white copper alloy of the invention represents a silver-white color equivalent to that of nickel silver while drastically reducing the content of Ni, and thus can suppress Ni allergy as much as possible even in the use subject to direct human contact.
  • Press formability, machinability, torsion strength, tarnish resistance, bending property, impact resistance, stress corrosion cracking resistance, wear resistance, and the like are excellent, a hot process (hot rolling process, hot extruding process) can be performed, cost performance is excellent and a practical value is high.
  • Pb and Bi in general, when the content is equal to or less than 0.1 mass%, they are not harmful to human bodies.
  • the content is equal to or less than 0.014 mass%, the upper limit of a more preferable range, there is hardly any problem.
  • the copper alloy containing no Pb or a very small amount of Pb even though contained can be applied to the applications where health and sanitary are particularly important, similar to the copper alloy containing no Pb, and it is possible to further improve machinability or the like.
  • the production method of the invention in any case of a rolling production method and a casting production method, it is possible to appropriately produce the copper alloy.
  • Example Alloy silver-white copper alloys
  • Example Alloy No. 101 to No. 104, No. 201 to No. 215, No. 301 to No. 303, No. 401, No. 402, No. 701, No. 702, No. 901, No. 902, No. 1401 to No. 1408, No. 1501 to No. 1509, No. 1701 to No. 1706, No. 1801 to No. 1813, No. 1901, No. 1902, No. 2001 to No. 2003, No. 2301, No. 2302, No. 2501, and No. 2502 according to the invention.
  • Each of the hot processed raw material A has an alloy composition shown in Table 1 or Table 2, and is a rolled plate material with a thickness of 12 mm obtained by heating a plate-shaped ingot with a thickness of 190 mm, a width of 630 mm, and a length of 2000 mm to 800°C and performing a hot rolling process.
  • Each of the hot processed raw material B has an alloy composition shown in Table 2 or Table 3, and is a hot extruded rod material with a diameter of 23 mm obtained by performing face milling on a cylindrical ingot with a diameter of 100 m and a length of 150 mm to be a diameter of 96 mm, heating it to 800°C, and performing a hot extruding process.
  • Each of the continuously cast raw material C has an alloy composition shown in Table 3 or Table 4, and is a cast plate with a thickness of 40 mm, a width of 100 mm, and a length of 200 mm obtained by performing a continuous casting process using a horizontal continuous casting machine.
  • Each of the continuously cast raw material D has an alloy composition shown in Table 4 or Table 5, and is a cast plate with a thickness of 15 mm, a width of 100 mm, and a length of 200 mm obtained by performing a continuous casting process using a horizontal continuous casting machine.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-1 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 650°C for 12 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material A1-1 was subjected to face milling to be as thick as 11 mm, it was subjected to a cold rolling process that is a first cold process, and a first cold processed material A2-1 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-1 was subjected to a second heat treatment (final heat treatment), and a second heat treated material A3-1 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material A2-1 at 565°C for 16 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-1 was subjected to a second cold rolling process, and Example Alloys No. 101 to No. 104 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-2 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material A1-2 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-2 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-2 was subjected to a second heat treatment (final heat treatment), and a second heat treated material A3-2 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material A2-2 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-2 was subjected to a second cold rolling process, and Example Alloys No. 201 to No. 215 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processedg raw material A was subjected to a first heat treatment, and a first heat treated material A1-3 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C and keeping it at 530°C for 1 hour during the cooling (it is kept at 530°C during cooling down to 500°C and is cooled at 0.4°C/minute down to 500°C. Re-heating to 530°C is not performed.).
  • the first heat treated material A1-3 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-3 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-3 was subjected to a second heat treatment (final heat treatment), and a second heat treated material A3-3 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material A2-3 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 530°C, keeping it at 530°C for 1 hour, and cooling it at an average cooling rate of 0.3°C/minute down to 500°C (the same as the part described in the paragraph [0058]), that is, a cooling process of slowing cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-3 was subjected to a second cold rolling process, and Example Alloys No. 301 to No. 303 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-4 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 650°C for 12 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material A1-4 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-4 with a thickness of 5 mm was obtained.
  • the processing rate is 55%.
  • the first cold processed material A2-4 was subjected to a second heat treatment, and a second heat treated material A3-4 was obtained.
  • This heat treatment includes a heating process of heating the first-order cold processed material A2-4 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-4 was subjected to a second cold rolling process, and a second cold processed material A4-4 with a thickness of 3.25 mm was obtained.
  • the processing rate is 35%.
  • the second cold processed material A4-4 was subjected to a third heat treatment (final heat treatment), and a third heat treated material A5-4 was obtained.
  • This heat treatment includes a heating processing of heating the second cold processed material A4-4 at 565°C for 8 hours, and a cooling process of slowing cooling it at an average cooling rate 0.3°C/minute down to 500°C.
  • the third heat treated material A5-4 was subjected to a third cold rolling process, and Example Alloys No. 401 and No. 402 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material A was subjected to a first cold rolling process without performing a heat treatment, unlike Processes M1 to M4. That is, the raw material A was subjected to face milling to be as thick as 11 mm, it was subjected to the first cold rolling process, and a first cold processed material A2-5 with a thickness of 3.25 mm was obtained. In this case, the processing rate is 70%.
  • the first cold processed material A2-5 was subjected to a heat treatment, and a heat treated material A3-5 was obtained.
  • This heat treatment includes a heating processed of heating the first cold processed material A2-5 at 575°C for 3 hours, and a cooling process of slowing cooling it at an average cooling rate 0.3°C/minute down to 500°C.
  • the heat treated material A3-5 was subjected to a second cold rolling process, and reference Example Alloys No. 501 to No. 503 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-6 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 540°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material A1-6 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-6 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-6 was subjected to a second heat treatment, and a second heat treated material A3-6 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material A2-6 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-6 was subjected to a second cold rolling process, and Reference Example Alloys No. 601 and No. 602 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-7 was obtained.
  • the raw material A was heated at 675°C for 6 hours and was air-cooled. In this air cooling, an average cooling rate down from 675°C to 500°C was 10°C/minute.
  • the first heat treated material A1-7 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-7 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-7 was subjected to a second heat treatment, and a second heat treated material A3-7 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material A2-7 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-7 was subjected to a second cold rolling process, and Example Alloys No. 701 and No. 702 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • Example Alloy compositions of Example Alloys No. 701 and No. 702 which are the hot processed materials (hot rolled materials) obtained as described above are as shown in Table 2.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-8 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material A1-8 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-8 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-8 was subjected to a second heat treatment (490°C, 8 hours), and a second heat treatment A3-8 was obtained.
  • the second heat treated material A3-8 was subjected to a second cold rolling process, and reference Example Alloys No. 801 and No. 802 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material A was subjected to a first heat treatment, and a first heat treated material A1-9 was obtained.
  • This heat treatment includes a heating process of heating the raw material A at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material A1-9 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material A2-9 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material A2-9 was subjected to a second heat treatment, and a second heat treated material A3-9 was obtained.
  • This heat treatment includes a heating process of heating the first-order cold processed material A2-9 at 530°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material A3-9 was subjected to a second cold rolling process, and Example Alloys No. 901 and No. 902 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material B was subjected to a first heat treatment, and a first heat treated material B1-1 was obtained.
  • This heat treatment includes a heating process of heating the raw material B at 620°C for 12 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material B1-1 was subjected to pickling, it was subjected to a drawing process that is a first cold process, and a first cold processed material B2-1 with a diameter of 16.5 mm was obtained.
  • the processing rate is 49%.
  • the first cold processed material B2-1 was subjected to a second heat treatment, and a second heat treated material B3-1 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material B2-1 at 560°C for 16 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material B3-1 was subjected to a second drawing process, and reference Example Alloys No. 1001 to No. 1007 with a diameter of 14.5 mm were obtained. In this case, the processing rate is 23%.
  • the hot processed raw material B was subjected to a first heat treatment, and a first heat treated material B1-2 was obtained.
  • This heat treatment includes a heating process of heating the raw material B at 635°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material B1-2 was subjected to pickling, it was subjected to a first drawing process, and a first cold processed material B2-2 with a diameter of 16.5 mm was obtained.
  • the processing rate is 49%.
  • the first cold processed material B2-2 was subjected to a second heat treatment, and a second heat treated material B3-2 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material B2-2 at 575°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material B3-2 was subjected to a second drawing process, and reference Example Alloys No. 1101 to No. 1108 with a diameter of 14.5 mm were obtained. In this case, the processing rate is 23%.
  • the hot processed raw material B was subjected to a first drawing process without performing a heat treatment, unlike Processes M11 and M12. That is, the raw material B was subjected to pickling, it was subjected to the first drawing process, and a first cold processed material B2-3 with a diameter of 16.5 mm was obtained. In this case, the processing rate is 49%.
  • the first cold processed material B2-3 was subjected to a heat treatment, and a heat treated material B3-3 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material B2-3 at 560°C for 16 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material B3-3 was subjected to a second drawing process, and reference Example Alloys No. 1201 and No. 1202 with a diameter of 14.5 mm were obtained. In this case, the processing rate is 23%.
  • the hot processed raw material B was subjected to a first heat treatment (490°C, 12 hours), and a first heat treated material B1-4 was obtained.
  • the first heat treated material B1-4 was subjected to pickling, it was subjected to a first drawing process, and a first cold processed material B2-4 with a diameter of 16.5 mm was obtained.
  • the processing rate is 49%.
  • the first cold processed material B2-4 was subjected to a second heat treatment, and a second heat treated material B3-4 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material B2-4 at 560°C for 16 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material B3-4 was subjected to a second drawing process, and reference Example Alloys No. 1301 and No. 1302 with a diameter of 14.5 mm were obtained. In this case, the processing rate is 23%.
  • the cast raw material C was subjected to a first heat treatment, and a first heat treated material C1-1 was obtained.
  • This heat treatment includes a heating process of heating the raw material C at 670°C for 12 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material C1-1 was subjected to face milling to be as thick as 36 mm, it was subjected to a cold rolling process that is a first cold process, and a first cold processed material C2-1 with a thickness of 18 mm was obtained.
  • the processing rate is 50%.
  • the first cold processed material C2-1 was subjected to a second heat treatment (final heat treatment), and a second heat treated material C3-1 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material C2-1 at 565°C for 16 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material C3-1 was subjected to a second cold rolling process, and Example Alloys No. 1401 to No. 1408 with a thickness of 14.5 mm were obtained. In this case, the processing rate is 19%.
  • the cast raw material C was subjected to a first heat treatment, and a first heat treated material C1-2 was obtained.
  • This heat treatment includes a heating process of heating the raw material C at 700°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material C1-2 was subjected to face milling to be as thick as 36 mm, it was subjected to a first cold rolling process, and a first cold processed material C2-2 with a thickness of 18 mm was obtained.
  • the processing rate is 50%.
  • the first cold processed material C2-2 was subjected to a second heat treatment (final heat treatment), and a second heat treated material C3-2 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material C2-2 at 580°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material C3-2 was subjected to a second cold rolling process, and Example Alloys No. 1501 to No. 1509 with a thickness of 14.5 mm were obtained. In this case, the processing rate is 19%.
  • the hot processed raw material C was subjected to a first cold rolling process without performing a heat treatment, unlike Processes M14 and M15. That is, the raw material C was subjected to face milling to be as thick as 36 mm, it was subjected to the first cold rolling process, and a first cold processed material C2-3 with a thickness of 18 mm was obtained. In this case, the processing rate is 50%.
  • the first cold processed material C2-3 was subjected to a heat treatment, and a heat treated material C3-3 was obtained.
  • This heat treatment includes a heating processing of heating the first cold processed material C2-3 at 580°C for 6 hours, and a cooling process of slowing cooling it at an average cooling rate 0.3°C/minute down to 500°C.
  • the heat treated material C3-3 was subjected to a second cold rolling process, and reference Example Alloys No. 1601 and No. 1602 with a thickness of 14.5 mm were obtained. In this case, the processing rate is 19%.
  • the cast raw material D was subjected to a first heat treatment, and a first heat treated material D1-1 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 650°C for 12 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material D1-1 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material D2-1 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-1 was subjected to a second heat treatment (final heat treatment), and a second heat treated material D3-1 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-1 at 565°C for 16 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treatment D3-1 was subjected to a second cold rolling process, and Example Alloys No. 1701 to No. 1706 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the cast raw material D was subjected to a first heat treatment, and a first heat treated material D1-2 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material D1-2 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material D2-2 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-2 was subjected to a second heat treatment (final heat treatment), and a second heat treated material D3-2 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-2 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material D3-2 was subjected to a second cold rolling process, and Example Alloys No. 1801 to No. 1813 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the cast raw material D was subjected to a first heat treatment, and a first heat treated material D1-3 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C and keeping it at 530°C for 1 hour during the cooling (it is kept at 530°C during cooling down to 500°C and is cooled at 0.4°C/minute down to 500°C. Re-heating to 530°C is not performed.).
  • the first heat treated material D1-3 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material D2-3 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-3 was subjected to a second heat treatment (final heat treatment), and a second heat treated material D3-3 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-3 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 530°C, keeping it at 530°C for 1 hour, and cooling it at an average cooling rate of 0.3°C/minute down to 500°C (the same as the part described in the paragraph [0058]).
  • the second heat treated material D3-3 was subjected to a second cold rolling process, and Example Alloys No. 1901 and No. 1902 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material D was subjected to a first heat treatment, and a first heat treated material D1-4 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 650°C for 12 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material D1-4 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material D2-4 with a thickness of 5 mm was obtained.
  • the processing rate is 55%.
  • the first cold processed material D2-4 was subjected to a second heat treatment, and a second heat treated material D3-4 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-4 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material D3-4 was subjected to a second cold rolling process, and a second cold processed material D4-4 with a thickness of 3.25 mm was obtained.
  • the processing rate is 35%.
  • the second cold processed material D4-4 was subjected to a third heat treatment (final heat treatment), and a third heat treated material D5-4 was obtained.
  • This heat treatment includes a heating process of heating the second cold processed material D4-4 at 565°C for 8 hours, and a cooling process of slowing cooling it at an average cooling rate 0.3°C/minute down to 500°C.
  • the third heat treated material D5-4 was subjected to a third cold rolling process, and Example Alloys No. 2001 to No. 2003 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material D was subjected to a first cold rolling process without performing a heat treatment, unlike Processes M17 to M20. That is, the raw material D was subjected to face milling to be as thick as 11 mm, it was subjected to the first cold rolling process, and a first cold processed material D2-5 with a thickness of 3.25 mm was obtained. In this case, the processing rate is 70%.
  • the first cold processed material D2-5 was subjected to a heat treatment, and a heat treated material D3-5 was obtained.
  • This heat treatment includes a heating processing of heating the first cold processed material D2-5 at 575°C for 3 hours, and a cooling process of slowing cooling it at an average cooling rate 0.3°C/minute down to 500°C.
  • the heat treated material D3-5 was subjected to a second cold rolling process, and Reference Example Alloys No. 2101 to No. 2105 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the cast raw material D was subjected to a first heat treatment, and a first heat treated material D1-6 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 540°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material D1-6 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material D2-6 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-6 was subjected to a second heat treatment (final heat treatment), and a second heat treated material D3-6 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-6 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material D3-6 was subjected to a second cold rolling process, and Reference Example Alloys No. 2201 and No. 2202 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material D was subjected to a first heat treatment, and a first heat treated material D1-7 was obtained.
  • the raw material D was heated at 675°C for 6 hours and was air-cooled. In this air cooling, an average cooling rate down to 500°C from 675°C was 10°C/minute.
  • the first heat treated material D1-7 was subjected to face milling to be as thick as 11 mm, it was subjected to a first cold rolling process, and a first cold processed material D2-7 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-7 was subjected to a second heat treatment, and a second heat treated material D3-7 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-7 at 575°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C. That is, a cooling process of slowing cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material D3-7 was subjected to a second cold rolling process, and Example Alloys No. 2301 and No. 2302 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material D was subjected to a first heat treatment, and a first heat treated material D1-8 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material D1-8 was subjected to face milling to be as thick as 11 mm, it was subjected to a cold rolling process that is a first cold process, and a first cold processed material D2-8 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-8 was subjected to a second heat treatment (490°C, 8 hours), and a second heat treatment D3-8 was obtained.
  • the second heat treated material D3-8 was subjected to a second cold rolling process, and reference Example Alloys No. 2401 to No. 2403 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • the hot processed raw material D was subjected to a first heat treatment, and a first heat treated material D1-9 was obtained.
  • This heat treatment includes a heating process of heating the raw material D at 675°C for 6 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.4°C/minute down to 500°C.
  • the first heat treated material D1-9 was subjected to face milling to be as thick as 11 mm, it was subjected to a cold rolling process that is a first cold process, and a first cold processed material D2-9 with a thickness of 3.25 mm was obtained.
  • the processing rate is 70%.
  • the first cold processed material D2-9 was subjected to a second heat treatment, and a second heat treated material D3-9 was obtained.
  • This heat treatment includes a heating process of heating the first cold processed material D2-9 at 530°C for 3 hours, and a cooling process of slowly cooling it at an average cooling rate of 0.3°C/minute down to 500°C.
  • the second heat treated material D3-9 was subjected to a second cold rolling process, and Example Alloys No. 2501 and No. 2502 with a thickness of 2.6 mm were obtained. In this case, the processing rate is 20%.
  • Comparative Example Alloy copper alloys (hereinafter, referred to as "Comparative Example Alloy") No. 3001 to No. 3008, No. 3101 to No. 3108, No. 3201 to No. 3203, No. 3301, No. 3302, No. 3401, No. 3402, No. 3501 to No. 3503, No. 3601 to No. 3603, No. 3701 to No. 3707, No. 3801, and No. 3901 to No. 3906 shown in Table 6 and Table 7 were obtained.
  • Comparative Example Alloys No. 3001 to No. 3008 are hot processed materials (hot rolled materials) produced by the same process as Process M2 of the examples, using the hot processed raw material A having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3001 to No. 3008 and the raw material A used to produce the same are as shown in Table 6.
  • Comparative Example Alloys No. 3101 to No. 3108 are hot processed materials (hot rolled materials) produced by the same process as Process M5 of the examples, using the hot processed raw material A having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3101 to No. 3108 and the raw material A used to produce the same are as shown in Table 6.
  • Comparative Example Alloys No. 3201 to No. 3203 are hot processed materials (hot extruded materials) produced by the same process as Process M10 of the examples, using the hot processed raw material B having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3201 to No. 3203 and the raw material B used to produce the same are as shown in Table 6.
  • Comparative Example Alloys No. 3301 and No. 3302 are hot processed materials (hot extruded materials) produced by the same process as Process M12 of the examples, using the hot processed raw material B having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3301 and No. 3302 and the raw material B used to produce the same are as shown in Table 6.
  • Comparative Example Alloys No. 3401 and No. 3402 are continuously cast materials produced by the same process as Process M14 of the examples, using the continuously cast raw material C having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3401 and No. 3402 and the raw material C used to produce the same are as shown in Table 7.
  • Comparative Example Alloys No. 3501 to No. 3503 are continuously cast materials produced by the same process as Process M15 of the examples, using the continuously cast raw material C having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3501 to No. 3503 and the raw material C used to produce the same are as shown in Table 7.
  • Comparative Example Alloys No. 3601 to No. 3603 are continuously cast materials produced by the same process as Process M16 of the examples, using the continuously cast raw material C having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3601 to No. 3603 and the raw material C used to produce the same are as shown in Table 7.
  • Comparative Example Alloys No. 3701 to No. 3707 are continuously cast materials produced by the same process as Process M18 of the examples, using the continuously cast raw material D having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloys No. 3701 to No. 3707 and the raw material D used to produce the same are as shown in Table 7.
  • Comparative Example Alloy No. 3801 is a continuously cast material produced by the same process as Process M21 of the examples, using the continuously cast raw material D having the same shape obtained by the same process as that of the examples except for the difference in alloy composition. Alloy compositions of Comparative Example Alloy No. 3801 and the raw material D used to produce the same are as shown in Table 7.
  • Comparative Example Alloys No. 3901 to No. 3903 are commercially available temper-"H" materials with a thickness of 2.4 mm whose compositions are shown in Table 7.
  • Comparative Example Alloys No 3904 to No. 3906 are commercially available rod materials with a diameter of 15 mm put whose compositions are shown in Table 5. Based on the alloy compositions, No. 3901 and No. 3904 corresponds to CDA C79200.
  • No. 3902, No.3903, No.3905 and No.3906 correspond to JIS C3710, JIS C2801, JIS C3712, and JIS C2800, respectively.
  • Fig. 1 and Fig. 2 are photographs of an etching surface of Example Alloy No. 201.
  • Fig. 1 shows a metal structure of the hot processed raw material A, and it is understood from Fig. 1 that ⁇ phases in the raw materials A are in a net-like fashion.
  • Fig. 2 shows a metal structure of the first heat treated material A1-2 obtained by performing a heat treatment at 675°C on the raw material A. It is understood from Fig. 2 that the net-like structure of ⁇ phases is disappeared (segmentalized) by the high temperature heat treatment, that the ⁇ phases are dispersed, and that a ratio occupied by ⁇ phases is lowered by the precipitation of ⁇ phases.
  • Fig. 3 and Fig. 4 are photographs of an etching surface of the raw material A of Example Alloy No. 201, which is subjected to a heat treatment or a cold process different from Process M2. That is, Fig. 3 shows a metal structure of a heat treated material obtained by performing a heat treatment different from Process M2 (keeping at 540°C for 6 hours, slowly cooling at 0.4°C/minute down to 500°C, and then air-cooling) on the raw material A under a low temperature condition, and Fig. 4 shows a metal structure of a cold processed material obtained by performing the same cold rolling (processing rate 70%) as Process M2 without performing a heat treatment on the raw material A unlike Process M2. It is understood from Fig.
  • Fig. 5 is a photograph of an etching surface illustrating a metal structure of the first cold processed material A2-2 of Example Alloy No 201. It is understood from Fig. 5 that the amount of ⁇ phases is small and the ⁇ phases are elongated in a rolling direction by the cold rolling in the same manner as shown in Fig. 2 .
  • Fig. 6 is a photograph of an etching surface illustrating a metal structure of the second heat treated material A3-2 obtained by performing a heat treatment (575°C) on the first processed material A2-2 shown in Fig. 5 .
  • ⁇ phases are uniformly dispersed in ⁇ phases of matrix, and the shape and size (average value of long side/short side, etc.) are in the optimal formation as described above.
  • Fig. 7 is a photograph of an etching surface illustrating a metal structure of a heat treated material obtained by a heat treatment (490°C, 8 hours) at a low temperature unlike Process M2 on the cold processed materials (first cold processed material A2-2 of Example Alloy No. 201) shown in Fig. 5 . It is understood from Fig. 7 that precipitation caused by ⁇ phases is insufficient due to the low temperature heat treatment, that ⁇ phases are longitudinally continued, and on the other hand, the ⁇ phases are precipitated around grain boundaries, unlike the case shown in Fig. 6 .
  • Fig. 8 is a photograph of an etching surface illustrating a metal structure of a heat treated material obtained by performing a heat treatment (530°C, 3 hours, average cooling rate down to 500°C: 0.4°C/minute) under the condition of a temperature lower than the heat treatment temperature (575°C) of Process M2, on the cold processed material (first cold processed material A2-2 of Example Alloy No. 201) shown in Fig. 5 . It is understood from Fig.
  • Fig. 9 is an etching photograph illustrating a metal structure of a heat treated material obtained by performing a heat treatment (575°C, 3 hours, average cooling rate down to 500°C: 0.4°C/minute) under the same condition as Process M2, on the cold processed material (a raw material is subjected to a cold process without performing a heat treatment) shown in Fig. 4 . It is clearly understood from Fig.
  • Example Alloys and Comparative Example Alloys a ratio (hereinafter, referred to as "raw material ⁇ phase ratio") occupied by ⁇ phases in the raw materials A, B, C, and D, a long side/short side ratio (average value of long side/short side) of ⁇ phases, and the number of ⁇ phases (hereinafter, referred to as "the number of ⁇ phase of 0.5 mm or more”) having a long side of 0.5 mm or more per 0.1 mm 2 were measured.
  • raw material ⁇ phase ratio occupied by ⁇ phases in the raw materials A, B, C, and D
  • a long side/short side ratio average value of long side/short side
  • the number of ⁇ phases hereinafter, referred to as "the number of ⁇ phase of 0.5 mm or more” having a long side of 0.5 mm or more per 0.1 mm 2
  • the average grain size was measured according to an FE-SEM-EBSP (Electron Back Scattering diffraction Pattern) method. That is, FE-SEM is JSM-7000F manufactured by JEOL, Ltd., TSL solutions OIM-Ver. 5.1 was used for analysis, and the average grain size was measured from a grain size map (Grain Map) of 200-fold magnification and 500-fold magnification in analysis. A method of calculating the average grain size is based on a quadrature method (JIS H 0501).
  • the ratio ( ⁇ phase ratio) occupied by ⁇ phases was measured by the FE-SEM-EBSP method.
  • FE-SEM is JSM-7000F manufactured by JEOL, Ltd., OIM-VER. 5.1 manufacture by TSL solutions, Ltd. was used for analysis, and it was measured from a phase map (Phase Map) of 200-fold magnification and 500-fold magnification in analysis.
  • the length (long side, short side) and area of ⁇ phases were measured by the FE-SEM-EBSP method.
  • the maximum length, long side length, and short side length of ⁇ phases were calculated by binarization using the image processing software "WinROOF" from a phase map of 200-fold magnification and 500-fold magnification in analysis.
  • Example Alloys satisfy the above-described proper conditions about ⁇ phases and ⁇ phases.
  • the optimal range of less than 5 is represented by " ⁇ ”
  • the proper range of 5 to 10 although not optimal, is represented by " ⁇ ”
  • the range of over 10 out of the proper range is represented by "X”.
  • a macro structure of a cast material is obtained by pouring a melt into a permanent mold with an inner diameter of 40 mm and a height of 50 mm, polishing a transverse cross section of the cast material, and etching it with nitric acid to reveal the macro structure.
  • the macro structure was observed in an enlarged image at about 25-fold magnification from a real size, and an average grain size ("grain size of macro structure" represented in Tables) was measured by a comparison method.
  • Example Alloys and Comparative Example Alloys hot/cold workability, torsion strength, impact strength, bending property, wear resistance, press formability, machinability, and the like were verified as follows.
  • Hot workability was assessed by a crack condition (crack condition of raw materials A, B, C, and D) after hot rolling.
  • the results are shown in Tables 15 to 19 and Tables 25 and 26.
  • a case where no damage such as cracks and only minute cracks (5 mm or less) were observed is considered as excellent in practicality and is represented by " ⁇ ".
  • Another case where less than 10 pieces of edge cracks as large as 10 mm or less were observed throughout the whole length is considered as practical and is represented by " ⁇ ”.
  • Yet another case where large cracks of as large as 10 mm or more and/or more than 10 pieces of small cracks as large as 10 mm or less were observed is considered as impractical (significant rework is necessary) and is represented by "X".
  • torsion strength As for torsion strength, torsion test pieces (length: 320 mm, diameter of chuck portion: 14.1 mm, diameter of parallel portion: 7.8 mm, length of parallel portion: 100 mm) were taken from Example Alloys and Comparative Example Alloys. A torsion test was performed thereon, and torsion strength (hereinafter, referred to as "1° torsion strength") in case of permanent deformation of 1° and torsion strength (hereinafter, referred to as "45° torsion strength”) in case of permanent deformation of 45° were measured. The results are shown in Tables 6 to 10. Although a rod material and a plate material are different in shapes, it is impossible to insert a key in case it has only a slight deformation. It is impossible for a key to be repaired if the deformation reaches 45°, and there are concerns about safety as well. It was verified from the torsion test that the aforesaid problems not occur in Example Alloys.
  • Impact test pieces (V notch test piece based on JIS Z2242) were taken from Example Alloys and Comparative Example Alloys. Charpy impact test was performed thereon, and impact strength was measured. The results are shown in Tables 15 to 19 and Tables 25 and 26, and it was verified that Example Alloys satisfying the relational expressions f1 to f4 and the amount and shape of ⁇ phases are excellent in impact resistance.
  • Example Alloys satisfying the relational expressions f1 to f4 and the amount and shape of ⁇ phases have no problem in bending property.
  • bending property deteriorates when Cu concentration is low, the value of Mn/Ni is low, a ratio occupied by ⁇ phases is high, or the shape of ⁇ phases is not satisfactory.
  • Test pieces were taken from Example Alloys and Comparative Example Alloys.
  • An wear test was performed with a ball-on-disk wear tester (manufactured by Shinko Engineering Co., Ltd.). That is, the wear test was performed by using a SUS304 ball having a diameter of 10 mm as a sliding material under a load of 5 kgf (49N) without lubrication, which was subjected to a circumferential rotation wear at an wear rate of 0.1 m/min for a sliding distance of 250 m. Weights before and after the test were measured, thereby calculating a difference as an wear amount. The results are shown in Tables 15 to 19 and Tables 25 and 26, and it was verified that Example Alloys were excellent in wear resistance.
  • Example Copper Alloys and Comparative Example Copper Alloys are formed into a key-like shape by press (lateral clearance: 0.05 mm) using a T-shaped mold in order to assess press formability from a length of shear droop, size (length) of burr, and a dimensional difference of a product (at the fractured section) (whether or not the product is straightly pressed with high precision).
  • the results are shown in Tables 15 to 19 and Tables 25 and 26.
  • shear droop a case where an area of shear droop is 0.18 mm or less (7% of plate thickness) was considered as satisfactory in press formability, and is represented by " ⁇ "
  • burr a case where no burr (blister) was observed is considered as satisfactory in press formability and is represented by " ⁇ ".
  • a height of burr was less than 0.01 mm is considered as possible fair in formability and is represented by " ⁇ ", and yet another case where a height of burr is more than 0.01 mm is considered as poor in press formability and is represented by "X”.
  • a dimensional difference a case where the dimensional difference is 0.07 or less is considered as satisfactory in press formability and is represented by " ⁇ ”.
  • Another case where the dimensional difference is over 0.07 mm and less than 0.11 mm is considered as fair in press formability and is represented by " ⁇ ”
  • Example Alloys satisfy such requirements.
  • dimensional precision and the like it is preferable that 75% or more of a fractured surface is shear or a fracture surface.
  • a ratio occupied by a fracture surface was 75% or more. Needless to say, tool life is improved when a larger amount of fracture surfaces is present.
  • Drill test pieces (plate with thickness of 14.5 mm and rod with diameter of 14.5 mm) were taken from Example Alloys and Comparative Example Alloys.
  • a drill test was performed with no lubrication, and the torque of the drill was measured. That is, drilling was performed using a JIS standard drill manufactured by HUYS Industries Limited to drill a hole with a diameter of 3.5 mm and a depth of 10 mm at 1250 rpm and a feeding rate of 0.07 mm/rev, and a torque caused by the drilling was converted into an electrical signal and was recorded with a recorder, and it was converted again into a torque.
  • the results are shown in Tables 20 to 24 and Tables 27 and 28.
  • Test pieces similar to the bending test pieces were taken from Example Alloys and Comparative Example Alloys.
  • a stress corrosion cracking test was performed using the test pieces bent to 90 degrees by a method prescribed in JIS. That is, the test pieces were exposed to ammonia using a solution of aqueous ammonia and water mixed in the same quantity, rinsed by sulfuric acid, and then checked whether or not cracks were observed with a 10-fold stereoscopic microscope in order to assess stress corrosion cracking resistance. The results are shown in Tables 20 to 24 and Tables 27 and 28 (represented by "stress corrosion cracking property" in Tables).
  • the invention alloys obtained by satisfying the compositions and the relational expressions f1 to f4 and the appropriate heat treatment provides properties necessary for a key or the like, such as press formability, hot/cold workability, bending property, torsion strength, impact strength, wear resistance, and corrosion resistance.
  • Example Alloys and Comparative Example Alloys Color tone of Example Alloys and Comparative Example Alloys was measured according to the method based on JIS Z 8729-1982, and the results are shown by using L, a, b color system prescribed in JIS Z 8729-1980 in Tables 20 to 24 and Tables 27 and 28. Specifically, values of L, a, and b were measured in a manner of SCI (including specular reflection light) using a spectrum colorimeter "CM-2002" manufactured by Minolta, Inc.
  • CM-2002 spectrum colorimeter manufactured by Minolta, Inc.
  • L chromaticness
  • a (plus direction: red, minus direction: green)
  • a (plus direction: red, minus direction: green)
  • a minus value becomes larger as the amount of added Ni becomes larger or the amount of added Mn becomes smaller. That is, to obtain silver-white color, it is preferable that at least the value of [Ni]+[Mn] is equal to or more than 13.
  • a salt spray test pursuant to JIS Z 2371 was performed to measure color. That is, 5% NaCl solution of 35°C (to be accurate 35 ⁇ 2°C) was sprayed onto a sample placed in a spray chamber. It was taken out after a predetermined time (24 hours), and color measurement was conducted by the colorimeter. The results are shown in Tables 20 to 24 and Tables 27 and 28.
  • the aforesaid method of measuring color based on JIS Z 8722-1982 was additionally conducted on the sample subjected to the salt spray test, and the color variation after the salt spray test was verified.
  • the results are shown in Tables 20 to 24 and Tables 27 and 28 (represented by "color difference before and after test” in the Tables).
  • the L (chromaticness) is decreased by salt spray, and luster is lost.
  • the values of a and b moves into the plus direction, and color tone such as reddish brown becomes stronger. That is, due to the general corrosion resulting from salt spray and the reddish brown corrosion product such as copper oxide, luster is lost, and red color tone becomes stronger.
  • the degree of such color variation is remarkable as the total amount of added Ni and Mn becomes small.
  • Hot Processing Property Cold Processing Property Torsion Strength Impact Strength J/cm 2
  • Bending Wear Resistance J/cm 2
  • Press Formability 1° Permanent Deformation (N/mm 2 )
  • 45° Permanent Deformation N/mm 2
  • Dimensional Difference Shear Droop Burr 1103 183 295 47.3 1104 180 291 47 1105 182 285 45 1106 183 293 49.2 1107 187 295 49 1108 185 290 47 1201 153 273 33.8 1202 157 276 29.8 1301 165 276 40.3

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Claims (5)

  1. Alliage de cuivre blanc-argent comprenant :
    47,5 à 50,5 % en masse de Cu;
    7,8 à 9,8 % en masse de Ni ;
    4,7 à 6,3 % en masse de Mn ; et
    éventuellement un ou plusieurs éléments sélectionnés parmi
    0,001 à 0,08 % en masse de Pb,
    0,001 à 0,08 % en masse de Bi,
    0,0001 à 0,009 % en masse de C,
    0,0001 à 0,007 % en masse d'S,
    0,01 à 0,5 % en masse d'Al,
    0,001 à 0,09 % en masse de P,
    0,005 à 0,035 % en masse de Zr, et
    0,001 à 0,03 % en masse de Mg ;
    le restant étant Zn et des impuretés inévitables,
    dans lequel l'alliage de cuivre blanc-argent a une composition d'alliage satisfaisant les relations de f1 = [Cu] + 1,4 x [Ni] + 0,3 x [Mn] = 62,0 à 64,0, f2 = [Mn]/ [Ni] = 0,49 à 0,68, et f3 = [Ni] + [Mn] = 13,0 à 15,5 parmi une teneur [Cu] en % en masse de Cu, une teneur [Ni] en % en masse de Ni, et une teneur [Mn] en % en masse de Mn, et a une structure métallique dans laquelle des phases β à un rapport de surface de 2 à 17 % sont dispersées dans une matrice de phase α, dans lequel une taille moyenne de grain de phases a est de 0,003 à 0,018 mm, une surface moyenne des phases β est de 4x10-6 à 80x10-6 mm2, une valeur moyenne de côté long/coté court de phases β est de 2 à 7, et un rapport des phases β ayant une valeur de côté long/côté court de 12 ou moins sur le total des phases β est de 95 % ou plus ou le nombre des phases β ayant un côté long qui est de 0,06 mm ou plus n'est pas plus de 10 par 0,1 mm2.
  2. Alliage de cuivre blanc-argent selon la revendication 1, comprenant un ou plusieurs éléments sélectionnés parmi 0,001 à 0,08 % en masse de Pb, 0,001 à 0,08 % en masse de Bi, 0,0001 à 0,009 %en masse de C, et 0,0001 à 0,007 % en masse de S; dans lequel une relation de f5 = [β]+ 10 x ([Pb] - 0,001)1/2 + 10 x ([Bi] - 0,001)1/2 + 15 x ([C] - 0,0001)1/2 + 15 × ([S] - 0.0001)1/2 = 2 à 19 est satisfaite parmi le rapport de surface [β] en % des phases β, une teneur [Pb] en % en masse de Pb, une teneur [Bi] en % en masse de Bi, une teneur [C] en % en masse de C, et une teneur [S] en % en masse de S.
  3. Utilisation de l'alliage de cuivre blanc-argent selon la revendication 1 ou 2, comme un matériau constitutif d'une clé, d'une ébauche de clé, ou d'un produit de presse.
  4. Procédé de production de l'alliage de cuivre blanc-argent selon la revendication 1 ou 2, comprenant soumettre une matière première traitée à chaud ou une matière première en coulage continu à un traitement thermique, incluant un chauffage à une température de 600 à 760 °C pour une durée de 2 à 36 heures et un refroidissement à une vitesse de refroidissement moyenne de 1 °C/minute ou moins jusqu'à 500 °C, et un laminage à froid avec une réduction de 25 % ou plus.
  5. Procédé de production de l'alliage de cuivre blanc-argent selon la revendication 4, dans lequel le procédé comprend soumettre le matériau traité à chaud et laminé à froid à un traitement thermique à une température de 550 à 625 °C pour une durée de 2 à 36 heures, et un laminage à froid avec une réduction de 50% ou moins.
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CN101952469A (zh) 2011-01-19
JPWO2009113489A1 (ja) 2011-07-21
CN101952469B (zh) 2012-12-19
KR101146356B1 (ko) 2012-05-17
KR20100099331A (ko) 2010-09-10
JP4523999B2 (ja) 2010-08-11
WO2009113489A1 (fr) 2009-09-17
US8147751B2 (en) 2012-04-03
EP2278033A1 (fr) 2011-01-26
EP2278033A4 (fr) 2014-06-25
US20110097238A1 (en) 2011-04-28

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